Polyolefin composition

ABSTRACT

A polyolefin composition comprises a polypropylene polymer, 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, and an ester composition or an amide compound.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims, pursuant to 35 U.S.C. § 119(e)(1), priority toand the benefit of the filing date of U.S. Patent Application No.62/274,086 filed on Dec. 31, 2016, which application is herebyincorporated by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This application relates to polyolefin compositions comprising acombination of a clarifying agent and an ester composition or acombination of a clarifying agent and an amide compound.

BRIEF SUMMARY OF THE INVENTION

The invention generally provides polyolefin (e.g., polypropylene)compositions exhibiting improved (i.e., lower) haze levels. Thepolyolefin compositions generally comprise a combination of a clarifyingagent and an ester composition or a combination of a clarifying agentand an amide compound.

In a first embodiment, the invention provides a polyolefin compositioncomprising:

(a) a polyolefin polymer;

(b) 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol; and

(c) an ester composition comprising ester compounds, wherein at least aportion of the ester compounds are an ester of 1,2,3-propanetriol and atleast one fatty acid selected from the group consisting of C₁₄-C₂₂ fattyacids.

In a second embodiment, the invention provides a polyolefin compositioncomprising:

(a) a polyolefin polymer;

(b) 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol; and

(c) an amide compound selected from the group consisting of compoundsconforming to a structure of Formula (I) or Formula (X) below

wherein R₁ and R₁₁ are independently selected from the group consistingof C₇-C₂₇ alkyl groups and C₇-C₂₇ alkenyl groups, and R₁₅ is selectedfrom the group consisting of C₁-C₈ alkanediyl groups.

DETAILED DESCRIPTION OF THE INVENTION

In a first embodiment, the invention broadly provides a polyolefincomposition comprising (a) a polyolefin polymer, (b)1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol; and (c) anester composition comprising ester compounds.

The polyolefin composition comprises a polyolefin polymer. Thepolyolefin polymer can be any suitable polyolefin, such as apolypropylene, a polyethylene, a polybutylene, apoly(4-methyl-1-pentene), and a poly(vinyl cyclohexane). In a preferredembodiment, the thermoplastic polymer is a polyolefin selected from thegroup consisting of polypropylene homopolymers (e.g., atacticpolypropylene homopolymer, isotactic polypropylene homopolymer, andsyndiotactic polypropylene homopolymer), polypropylene copolymers (e.g.,polypropylene random copolymers), polypropylene impact copolymers, andmixtures thereof. Suitable polypropylene copolymers include, but are notlimited to, random copolymers made from the polymerization of propylenein the presence of a comonomer selected from the group consisting ofethylene, but-1-ene (i.e., 1-butene), and hex-1-ene (i.e., 1-hexene). Insuch polypropylene random copolymers, the comonomer can be present inany suitable amount, but typically is present in an amount of less thanabout 10 wt. % (e.g., about 1 to about 7 wt. %). Suitable polypropyleneimpact copolymers include, but are not limited to, those produced by theaddition of a copolymer selected from the group consisting ofethylene-propylene rubber (EPR), ethylenepropylene-diene monomer (EPDM),polyethylene, and plastomers to a polypropylene homopolymer orpolypropylene random copolymer. In such polypropylene impact copolymers,the copolymer can be present in any suitable amount, but typically ispresent in an amount of from about 5 to about 25 wt. %. The polyolefinpolymers described above can be branched or cross-linked, such as thebranching or cross-linking that results from the addition of additivesthat increase the melt strength of the polymer.

The polyolefin polymer (e.g., polypropylene polymer) used in thecomposition can be a polymer that has been manufactured to possess theapparent melt viscosity, Melt Flow Rate, and/or Flow Rate Ratiodescribed below for the polyolefin composition. For example,polypropylene polymers suitable for use in the composition include thosemanufactured in such a manner that the polymer sold by the manufacturerpossesses one of the apparent melt viscosity values recited below forthe polyolefin composition. Alternatively, a virgin polypropylenepolymer that does not possess the desired characteristics can bemodified through the addition of one or more additives. For example, thepolymer can be combined with an organic peroxide or a vis-breaking agentand melt processed (e.g., extruded) in order to modify one or morecharacteristics of the polymer. Examples of organic peroxides suitablefor such use include but are not limited to:2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,3,6,6,9,9-pentamethyl-3-(ethyl acetate)-1,2,4,5-tetraoxycyclononane, tert-butyl hydroperoxide, hydrogen peroxide, dicumylperoxide, tert-butyl peroxy isopropyl carbonate, di-tert-butyl peroxide,p-chlorobenzoyl peroxide, dibenzoyl diperoxide, tert-butyl cumylperoxide, tert-butyl hydroxyethyl peroxide, di-tert-amyl peroxide,2,5-dimethylhexene-2,5-diperisononanoate, acetylcyclohexanesulphonylperoxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate,tert-butyl-perneodecanoate, tert-butylperpivalate, tert-amylperpivalate,bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide,bis(2-methylbenzoyl)peroxide, disuccinoyl peroxide, diacetyl peroxide,dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate,bis(4-chlorobenzoyl)peroxide, tert-butyl perisobutyrate, tert-butylpermaleate, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclo-hexane,1,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxyisopropylcarbonate, tert-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate,tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate,2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane,dicumyl peroxide, 2,5-dimethylhexane 2,5-di-tert-butylperoxid,3-tert-butylperoxy-3-phenyl phthalide, di-tert-amyl peroxide,α,α′-bis(tert-butylperoxyisopropyl)benzene,3,5-bis(tert-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di-tert-butylperoxide, 2,5-dimethylhexyne 2,5-di-tert-butyl peroxide,3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide.

When used as an additive to modify the characteristics of the polymervia melt processing of the polymer, the organic peroxide or vis-breakingagent can be present in the polymer composition (prior to meltprocessing) in any suitable amount. The suitable amount of organicperoxide will depend upon several factors, such as the particularpolymer that is used in the composition, the starting properties of thepolymer, and the desired change in the properties of the polymer. In apreferred embodiment, the organic peroxide can be present in the polymercomposition (prior to melt processing) in an amount of about 10 ppm ormore, about 50 ppm or more, or about 100 ppm or more, based on the totalweight of the polymer composition. In another preferred embodiment, theorganic peroxide can be present in the polymer composition (prior tomelt processing) in an amount of about 1 wt. % (10,000 ppm) or less,about 0.5 wt. % (5,000 ppm) or less, about 0.4 wt. % (4,000 ppm) orless, about 0.3 wt. % (3,000 ppm) or less, about 0.2 wt. % (2,000 ppm)or less, or about 0.1 wt. % (1,000 ppm) or less, about 0.05 wt. % (about500 ppm) or less based on the total weight of the polymer composition.Thus, in a series of preferred embodiments, the organic peroxide can bepresent in the polymer composition (prior to melt processing) in anamount of about 10 to about 5,000 ppm, about 50 to about 3,000 ppm,about 50 to about 2,000 ppm, or about 100 to about 1,000 ppm, based onthe total weight of the polymer composition. As will be understood bythose skilled in the art, the organic peroxide degrades and is consumedduring the melt processing of the polymer composition. Therefore, theamount of organic peroxide present in the polymer composition after meltprocessing likely will not fall within the ranges recited above, andtypically, the organic peroxide is not detectable in the polymercomposition after melt processing.

As noted above, the polyolefin composition comprises1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol. This compoundis an acetal that can be produced by the reaction of an alditol with asubstituted benzenecarbaldehyde compound. More specifically, thecompound can be produced by the reaction of approximately 1 mole ofD-glucitol with approximately 2 moles of3,4-dichlorobenzenecarbaldehyde. The1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol can be providedin any suitable physical form, but generally the compound is provided inthe form of a powder.

As noted above, the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol typically isprovided in the form of a powder, which powder contains many fineparticles. The particles present in the powder generally are groupedinto three different particle types of increasing size and complexity:primary particles; aggregates; and agglomerates. The primary particlesgenerally are single crystals of the compound or fragments of suchsingle crystals. The aggregates are comprised of two or more primaryparticles that have become strongly bound to each other. The aggregatescannot be reduced in size (e.g., reduced to their constituent primaryparticles) except through milling. The agglomerates are comprised ofseveral primary particles and/or aggregates that have become weaklyassociated or bound together. The agglomerates can be reduced in size(e.g., broken apart and reduced to their constituent primary particlesand/or aggregates) by the application of relatively modest mechanicalforces. For example, the agglomerates can be reduced in size upondispersion in a suitable liquid medium. The agglomerates typicallycontain relatively large voids within their interior dimensions, andthese voids are filled with air. When such agglomerates are dispersed inthe molten polymer during processing, the agglomerates break apart asthe compound dissolves in the molten polymer. The air trapped in thevoids can then become entrained in the molten polymer, and thisentrained air leads to the formation of defects (e.g., white specksand/or bubbles) in the polymer composition.

The powder can have any suitable particle size. However, in order tofacilitate dissolution of the compounds in the molten polymer andprevent the formation of defects (e.g., white specks or bubbles) in thepolymer composition, it is advantageous for the particles to have arelatively small particle size. In a preferred embodiment, the volumemean diameter (i.e., the D[4,3]) of the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol particles isabout 40 μm or less, about 35 μm or less, about 30 μm or less, or about25 μm or less. Further, the D₉₀ of the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol particlespreferably is about 80 μm or less, about 75 μm or less, about 70 μm orless, about 65 μm or less, about 60 μm or less, or about 55 μm or less.

The particle size of the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol can be measuredusing any suitable technique. For example, the particle size of thepowder can be measured via dynamic light scattering using one of themany commercially available instruments designed for such measurements.When a dynamic light scattering technique is used, a representativesample of the particles generally is dispersed in a liquid medium and asample of this liquid medium is introduced into the dynamic lightscattering instrument. Any suitable liquid medium can be used, but watergenerally is the preferred medium. In order to facilitate dispersion ofthe particles in the liquid medium, a surfactant, preferably a non-ionicsurfactant (e.g., an octylphenol surfactant), can be added to the waterand the resulting mixture (i.e., water, surfactant, and particles) canbe stirred for a sufficient time for the particles to disperse (e.g.,for 1-5 minutes).

The 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol can bepresent in the polyolefin composition in any suitable absolute amount.Typically, the amount of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thepolyolefin composition is about 250 parts-per-million (ppm) or morebased on the weight of the polymer (e.g., polypropylene polymer) presentin the polyolefin composition. Preferably, the amount of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thepolyolefin composition is about 500 ppm or more, about 750 ppm or more,about 1,000 ppm or more, about 1,250 ppm or more, or about 1,500 ppm ormore based on the weight of the polymer (e.g., polypropylene polymer)present in the polyolefin composition. The amount of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thepolyolefin composition typically is also about 4,000 ppm or less basedon the weight of the polymer (e.g., polypropylene polymer) present inthe polyolefin composition. Preferably, the amount of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thepolyolefin composition is about 3,500 ppm or less, about 3,000 ppm orless, about 2,750 ppm or less, about 2,500 ppm or less, about 2,250 ppmor less, or about 2,000 ppm or less based on the weight of the polymer(e.g., polypropylene polymer) present in the polyolefin composition.Thus, in a series of sequentially more preferred embodiments, the amountof 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present inthe polyolefin composition is about 250 ppm to about 4,000 ppm, about250 ppm to about 3,000 ppm, about 250 ppm to about 2,500 ppm, or about500 ppm to about 2,000 ppm based on the weight of the polymer (e.g.,polypropylene polymer) present in the polyolefin composition.

In certain possibly preferred embodiments, the polyolefin compositioncan comprise another acetal compound in addition to the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol. In aparticularly preferred embodiment, the polyolefin compositionadditionally comprises1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol. The1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol can be producedby the reaction of approximately 1 mole of D-glucitol with approximately2 moles of o-xylenecarbaldehyde. The1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol can be providedin any suitable physical form, but, as with the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, the compoundgenerally is provided in the form of a powder containing may fineparticles.

The particle size of the1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol can be the same(e.g., in terms of volume mean diameter, D₉₀, or both) as the particlesize of the 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitoldescribed above. Alternatively, the particle size of the1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol can be smaller(e.g., in terms of volume mean diameter, D₉₀, or both) than the particlesize of the 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol. Ina preferred embodiment, the volume mean diameter (i.e., the D[4,3]) ofthe 1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol particlesis about 40 μm or less, about 35 μm or less, about 30 μm or less, about25 μm or less, about 20 μm or less, about 15 μm or less, about 10 μm orless, or about 7.5 μm or less. Further, the D₉₀ of the1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol particlespreferably is about 80 μm or less, about 75 μm or less, about 70 μm orless, about 65 μm or less, about 60 μm or less, about 55 μm or less,about 50 μm or less, about 45 μm or less, about 40 μm or less, about 35μm or less, about 30 μm or less, about 25 μm or less, about 20 μm orless, about 15 μm or less, about 10 μm or less, or about 7.5 μm or less.

When present in the polyolefin composition, the1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol can be presentin any suitable amount. For example, the1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol can be presentin any of the amounts listed above for the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol. Alternatively,the combined amount of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol and1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol present in thecomposition can fall within any of the ranges described above for the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol.

When the composition comprises both1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol and1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol, the twocompounds can be present in the polyolefin composition in any suitablerelative amounts. For example, the ratio of the mass of1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol present in thecomposition to the mass of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thecomposition preferably can be about 9:1 or less, about 8:1 or less,about 7:1 or less, about 6:1 or less, about 5:1 or less, about 4:1 orless, or about 3:1 or less. The ratio of the mass of1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol present in thecomposition to the mass of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thecomposition preferably can be about 1:9 or more, about 1:8 or more,about 1:7 or more, about 1:6 or more, about 1:5 or more, about 1:4 ormore, or about 1:3 or more. In one preferred embodiment, the ratio ofthe mass of 1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitolpresent in the composition to the mass of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thecomposition is about 9:1 to about 1:9. In a series of sequentially morepreferred embodiments, the ratio of the mass of1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol present in thecomposition to the mass of1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thecomposition is about 8:1 to about 1:8, about 7:1 to about 1:7, about 6:1to about 1:6, about 5:1 to about 1:5, about 4:1 to about 1:4, or about3:1 to about 1:3.

The polyolefin composition comprises an ester composition, and the estercomposition comprises at least one ester compound. The ester compositioncan comprise a plurality of different ester compounds. Preferably, atleast a portion of the ester compounds present in the ester compositionare an ester of 1,2,3-propanetriol and at least one fatty acid selectedfrom the group consisting of C₁₄-C₂₂ fatty acids. The C₁₄-C₂₂ fatty acidcan be selected from the group consisting of saturated fatty acids andunsaturated fatty acids, with saturated fatty acids being particularlypreferred. In a preferred embodiment, at least a portion of the estercompounds present in the ester composition are an ester of1,2,3-propanetriol and at least one fatty acid selected from the groupconsisting of C₁₆-C₁₈ fatty acids, with C₁₆-C₁₈ saturated fatty acidsbeing particularly preferred. In another preferred embodiment, the estercomposition comprises about 80% or more monoester compounds, morepreferably about 85% or more monoester compounds, and most preferablyabout 90% or more monoester compounds. In a preferred embodiment, theester composition comprises 2,3-dihydroxypropyl octadecanoate. Morepreferably, the ester composition comprises about 50% or more2,3-dihydroxypropyl octadecanoate.

As noted above, the ester composition can comprise a plurality ofdifferent ester compounds. The presence of different ester compounds canbe due, at least in part, to the distribution of different chain lengthsin the fatty acid. For example, as is understood by those of ordinaryskill in the art, a composition comprising a C₁₈ fatty acid can alsocontain appreciable amounts of a C₁₆ fatty acid. Thus, in the embodimentin which the ester composition comprises 2,3-dihydroxypropyloctadecanoate, the ester composition can also contain2,3-dihydroxypropyl hexadecanoate. The amount of these related estercompounds present in the ester composition will depend, at least inpart, on the particular source of fatty acid that is used.Naturally-derived sources of fatty acids can have relatively highamounts (e.g., up to 40% or more) of these related fatty acids.

The ester composition can be present in the polyolefin composition inany suitable amount. Preferably, the ester composition is present in thepolyolefin composition in an amount of about 50 ppm or more, morepreferably about 100 ppm or more. In another preferred embodiment, theester composition is present in the polyolefin composition in an amountof about 5,000 ppm or less, more preferably about 4,000 ppm or less, andmost preferably about 3,000 ppm or less. Thus, in a particularlypreferred embodiment, the ester composition is present in the polyolefincomposition in an amount of about 50 ppm to about 5,000 ppm. In anotherparticularly preferred embodiment, the ester composition is present inthe polyolefin composition in an amount of about 100 ppm to about 3,000ppm.

In a second embodiment, the invention provides a polyolefin compositioncomprising (a) a polypropylene polymer; (b)1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol; and (c) anamide compound. The polypropylene polymer present in the composition canbe any of the polymers discussed above in connection with the firstembodiment of the invention. The1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol present in thepolyolefin composition can exhibit any of the characteristics describedabove in connection with the first embodiment of the invention and canbe present in the composition in any of the amounts described above inconnection with the first embodiment of the invention. Further, thepolyolefin composition can further comprise1,3:2,4-bis-O-[(3,4-dimethylphenyl)methylene]-D-glucitol, and thiscompound can be present in the polyolefin composition in any of theamounts described above in connection with the first embodiment of theinvention.

As noted above, the polyolefin composition of the second embodimentcomprises an amide compound. The polyolefin composition can alsocomprises a plurality of different amide compounds. Preferably, thepolyolefin composition comprises an amide compound selected from thegroup consisting of compounds conforming to a structure of Formula (I)or Formula (X)

In the structure of Formula (I) and Formula (X), R₁ and R₁₁ areindependently selected from the group consisting of C₇-C₂₇ alkyl groupsand C₇-C₂₇ alkenyl groups, and R₁₅ is selected from the group consistingof C₁-C₈ alkanediyl groups. In a preferred embodiment, the polyolefincomposition comprises an amide compound conforming to the structure ofFormula (I) wherein R₁ is selected from the group consisting of C₁₇-C₂₁alkenyl groups. In one preferred embodiment, the polyolefin compositioncomprises an amide compound conforming to the structure of Formula (I)wherein R₁ is (Z)-12-heneicosen-1-yl. In another preferred embodiment,the polyolefin composition comprises an amide compound conforming to thestructure of Formula (I) wherein R₁ is (Z)-8-heptadecen-1-yl. In anotherpreferred embodiment, the polyolefin composition comprises an amidecompound conforming to the structure of Formula (X) wherein R₁₁ isselected from the group consisting of C₇-C₂₇ alkyl groups, with C₁₅-C₂₁alkyl groups being particularly preferred. In another preferredembodiment, the polyolefin composition comprises an amide compoundconforming to the structure of Formula (X) wherein R₁₅ is selected fromthe group consisting of C₁-C₃ alkanediyl groups, with an ethane-1,2-diylgroup being particularly preferred. Thus, in a particularly preferredembodiment, the polyolefin composition comprises an amide compoundconforming to the structure of Formula (X) wherein each R₁₁ isheptadecan-1-yl and R₁₅ is ethane-1,2,-diyl.

As noted above, the polyolefin composition can comprise a mixture ofdifferent amide compounds. As with the ester compounds described in thefirst embodiment, the presence of these different amide compounds can bedue, at least in part, to the distribution of different chain lengths inthe fatty acid used in making the amide compound. Thus, a polyolefincomposition comprising an amide compound conforming to the structure ofFormula (I) wherein R₁ is (Z)-8-heptadecen-1-yl may also comprise anamide compound conforming to the structure of Formula (I) wherein R₁ isa C₁₅ alkenyl group. Further, the polyolefin composition can comprise amixture of one or more amide compounds conforming to the structure ofFormula (I) and one or more amide compounds conforming to the structureof Formula (X).

The amide compound can be present in the polyolefin composition in anysuitable amount. Preferably, the amide compound is present in thepolyolefin composition in an amount of about 50 ppm or more, morepreferably about 100 ppm or more. In another preferred embodiment, theamide compound is present in the polyolefin composition in an amount ofabout 5,000 ppm or less, more preferably about 4,000 ppm or less, andmost preferably about 3,000 ppm or less. Thus, in a particularlypreferred embodiment, the amide compound is present in the polyolefincomposition in an amount of about 50 ppm to about 5,000 ppm. In anotherparticularly preferred embodiment, the amide compound is present in thepolyolefin composition in an amount of about 100 ppm to about 3,000 ppm.When the polyolefin composition comprises more than one amide compound,each amide compound can be present in the composition in an amountfalling within the ranges described above, or the total amount of amidecompounds present in the polyolefin composition can fall within theranges described above. Preferably, the total amount of amide compoundspresent in the polyolefin composition falls within the ranges describedabove.

The polyolefin compositions described herein can have any suitableapparent melt viscosity. The apparent melt viscosity of the polyolefincomposition can be measured using any suitable method. For example, theapparent melt viscosity can be determining using the test methoddescribed in ASTM Test Method D3835-08 entitled “Standard Test Methodfor Determination of Properties of Polymeric Materials by Means of aCapillary Rheometer.” While this test method provides that 220° C. isthe testing temperature typically employed in testing polypropylenecompositions, a temperature of 190° C. is believed to be more suitabletemperature since it better approximates the lower processingtemperatures that are today employed with many commercial polymers.Thus, the apparent melt viscosities for the polypropylene-containingpolyolefin compositions listed herein preferably are determined usingthe above-referenced test method at a temperature of 190° C. Theapparent melt viscosity of the polyolefin composition can be measured atany suitable apparent shear rate. It is believed that an apparent shearrate of 100 s⁻¹ is preferred because it closely approximates the shearthat a polymer composition experiences during typical processingconditions. When measuring the apparent melt viscosity of the polyolefincomposition, the capillary rheometer preferably is equipped with a 1.00mm diameter capillary die with a length to diameter ratio of 30:1.Further, the polyolefin composition preferably is allowed to remain inthe capillary rheometer for a dwell time of six (6) minutes prior tobeginning the test. Lastly, the apparent melt viscosity of thepolyolefin composition preferably is determined after the polymer,1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, estercomposition and/or amide compound, and optional components have beenmelt processed (e.g., passed through an extruder).

Preferably, the polyolefin composition has an apparent melt viscosity ofabout 750 Pa·s or less at an apparent shear rate of 100 s⁻¹. Morepreferably, the polyolefin composition has an apparent melt viscosity ofabout 700 Pa·s or less, about 650 Pa·s or less, about 600 Pa·s or less,about 550 Pa·s or less, about 500 Pa·s or less, about 450 Pa·s or less,about 400 Pa·s or less, about 350 Pa·s or less, about 300 Pa·s or less,about 250 Pa·s or less, or about 200 Pa·s or less at an apparent shearrate of 100 s⁻¹ and a temperature of 190° C.

The polyolefin composition described herein can have any suitable MeltFlow Rate. The Melt Flow Rate of the polyolefin composition can bedetermined by any suitable method. For example, the Melt Flow Rate ofthe polyolefin composition can be determined using Procedure B in ASTMStandard D1238-10 entitled “Standard Test Method for Melt Flow Rates ofThermoplastics by Extrusion Plastometer.” The Melt Flow Rate of thepolyolefin composition preferably is measured using the aforementionedstandard test method. Preferably, the polyolefin composition has a MeltFlow Rate of 4 g/10 min or more. More preferably, the polyolefincomposition has a Melt Flow Rate of about 8 g/10 min or more, about 10g/10 min or more, about 12 g/10 min or more, about 20 g/10 min or more,about 35 g/10 min or more, or about 50 g/10 min or more. As in themeasurement of the apparent melt viscosity, the Melt Flow Rate of thepolyolefin composition preferably is determined after the polymer, the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, estercomposition and/or amide compound, and any optional components (e.g.,peroxide) have been melt processed (e.g., passed through an extruder).

As will be understood by those of ordinary skill in the art, thepolyolefin polymer will contain a population of discrete polymer chains,and those polymer chains will have varying lengths and molar masses. Thestatistical distribution of the lengths/molar masses of the polymerchains contained in the polymer is generally referred to as the molarmass distribution or molecular weight distribution. The polyolefinpolymers used in the compositions described herein can have any suitablemolar mass distribution. For example, the polyolefin polymer can have amolar mass distribution exhibiting a single mode or the molar massdistribution can exhibit a plurality of modes (e.g., bimodal, trimodal,etc.). The breadth of the molar mass distribution of a polymer can beexpressed using the polydispersity index. The polydispersity index iscalculated by measuring the number average molar mass and the massaverage molar mass (i.e., weight average molar mass) of the polymer, andthen dividing the mass average molar mass of the polymer by the numberaverage molar mass of the polymer. The result is a dimensionless unitthat quantifies the breadth of the molar mass distribution, with highervalues indicating greater breadth in the molar mass distribution. Thebreadth of the molar mass distribution can also be indirectly quantifiedby measuring and comparing the Melt Flow Rate of the polymer (or acomposition containing the polymer) under different conditions to yielda Flow Rate Ratio (FRR). This method is described, for example, inProcedure D of ASTM Standard D1238 entitled “Standard Test Method forMelt Flow Rates of Thermoplastics by Extrusion Plastometer.” Preferably,the FRR is calculated using the Melt Flow Rate measured using the 10 kgweight specified in the standard (MFR₁₀) and the Melt Flow Rate measuredusing the 2 kg weight specified in the standard (MFR₂). The polyolefincomposition described herein can have any suitable FRR. Preferably, thepolyolefin composition has a FRR (MFR₁₀/MFR₂) of about 17 or less. Morepreferably, the polyolefin composition has a FRR (MFR₁₀/MFR₂) of about16 or less or about 15 or less. As in measuring the apparent meltviscosity and the Melt Flow Rate, the Flow Rate Ratio of the polyolefincomposition preferably is determined after the polymer, the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, estercomposition and/or amide compound, and any optional components (e.g.,peroxide) have been melt processed (e.g., passed through an extruder).

The polyolefin compositions described herein can contain other polymeradditives in addition to the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol and estercomposition or amide compound. Suitable additional polymer additivesinclude, but are not limited to, antioxidants (e.g., phenolicantioxidants, phosphite antioxidants, and combinations thereof),anti-blocking agents (e.g., amorphous silica and diatomaceous earth),pigments (e.g., organic pigments and inorganic pigments) and othercolorants (e.g., dyes and polymeric colorants), fillers and reinforcingagents (e.g., glass, glass fibers, talc, calcium carbonate, andmagnesium oxysulfate whiskers), nucleating agents, clarifying agents,acid scavengers (e.g., metal salts of fatty acids, such as the metalsalts of stearic acid), polymer processing additives (e.g.,fluoropolymer polymer processing additives), polymer cross-linkingagents, slip agents (e.g., fatty acid amide compounds derived from thereaction between a fatty acid and ammonia or an amine-containingcompound), fatty acid ester compounds (e.g., fatty acid ester compoundsderived from the reaction between a fatty acid and a hydroxyl-containingcompound, such as glycerol, digylcerol, and combinations thereof), andcombinations of the foregoing.

As noted above, the polyolefin compositions can contain nucleatingagents in addition to the other components described above. Suitablenucleating agents include, but are not limited to,2,2′-methylene-bis-(4,6-di-tert-butylphenyl) phosphate salts (e.g.,sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenyl) phosphate oraluminum 2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate),bicyclo[2.2.1]heptane-2,3-dicarboxylate salts (e.g., disodiumbicyclo[2.2.1]heptane-2,3-dicarboxylate or calciumbicyclo[2.2.1]heptane-2,3-dicarboxylate), cyclohexane-1,2-dicarboxylatesalts (e.g., calcium cyclohexane-1,2-dicarboxylate, monobasic aluminumcyclohexane-1,2-dicarboxylate, dilithium cyclohexane-1,2-dicarboxylate,or strontium cyclohexane-1,2-dicarboxylate), and combinations thereof.For the bicyclo[2.2.1]heptane-2,3-dicarboxylate salts and thecyclohexane-1,2-dicarboxylate salts, the carboxylate moieties can bearranged in either the cis- or trans-configuration, with thecis-configuration being preferred.

As noted above, the polyolefin compositions can also contain one or moreadditional clarifying agents. Suitable clarifying agents include, butare not limited to, trisamides and acetal compounds that are thecondensation product of a polyhydric alcohol and an aromatic aldehyde.Suitable trisamide clarifying agents include, but are not limited to,amide derivatives of benzene-1,3,5-tricarboxylic acid, amide derivativesof 1,3,5-benzenetriamine, derivatives ofN-(3,5-bis-formylamino-phenyl)-formamide (e.g.,N-[3,5-bis-(2,2-dimethyl-propionylamino)-phenyl]-2,2-dimethyl-propionamide),derivatives of 2-carbamoyl-malonamide (e.g.,N,N′-bis-(2-methyl-cyclohexyl)-2-(2-methyl-cyclohexylcarbamoyl)-malonamide),and combinations thereof. As noted above, the clarifying agent can be anacetal compound that is the condensation product of a polyhydric alcoholand an aromatic aldehyde. Suitable polyhydric alcohols include acyclicpolyols such as xylitol and sorbitol, as well as acyclic deoxy polyols(e.g., 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol). Suitablearomatic aldehydes typically contain a single aldehyde group with theremaining positions on the aromatic ring being either unsubstituted orsubstituted. Accordingly, suitable aromatic aldehydes includebenzaldehyde and substituted benzaldehydes (e.g.,3,4-dimethyl-benzaldehyde or 4-propyl-benzaldehyde). The acetal compoundproduced by the aforementioned reaction can be a mono-acetal, di-acetal,or tri-acetal compound (i.e., a compound containing one, two, or threeacetal groups, respectively), with the di-acetal compounds beingpreferred. Suitable acetal-based clarifying agents include, but are notlimited to, the clarifying agents disclosed in U.S. Pat. Nos. 5,049,605;7,157,510; and 7,262,236.

The polyolefin compositions described herein can be produced by anysuitable method. For example, the polyolefin compositions can beproduced by simple mixing (e.g., high shear or high intensity mixing) ofthe polyolefin polymer, the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, the estercomposition and/or amide compound, and any additional optionalcomponents. Alternatively, the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol and the estercomposition and/or amide compound (as well as additional optionalcomponents, such as those described above) can be pre-blended to providean additive composition. This additive composition can then be mixedwith the polyolefin polymer to produce the polyolefin compositiondescribed above. The polyolefin composition can be provided in any formsuitable for use in further processing to produce an article. Forexample, the polyolefin composition can be provided in the form of apowder (e.g., free-flowing powder), flake, pellet, prill, tablet,agglomerate, and the like.

The polyolefin compositions described herein are believed to be usefulin producing thermoplastic articles. The polyolefin compositions can beformed into the desired thermoplastic article by any suitable technique,such as injection molding, injection rotational molding, blow molding(e.g., injection blow molding or injection stretch blow molding),extrusion (e.g., sheet extrusion, film extrusion, cast film extrusion,or foam extrusion), extrusion blow molding, thermoforming, rotomolding,film blowing (blown film), film casting (cast film), and the like.

The polyolefin compositions described herein can be used to produce anysuitable article or product. Suitable products include, but are notlimited to, medical devices (e.g., pre-filled syringes for retortapplications, intravenous supply containers, and blood collectionapparatus), food packaging, liquid containers (e.g., containers fordrinks, medications, personal care compositions, shampoos, and thelike), apparel cases, microwavable articles, shelving, cabinet doors,mechanical parts, automobile parts, sheets, pipes, tubes, rotationallymolded parts, blow molded parts, films, fibers, and the like.

The following examples further illustrate the subject matter describedabove but, of course, should not be construed as in any way limiting thescope thereof.

Example 1

This example demonstrates the production of a polyolefin composition asdescribed above and the properties of the resulting polyolefincomposition.

Thirteen one-kilogram batches of a polypropylene random copolymercomposition (Samples 1A-1C and Samples 2A-2J) were compounded inaccordance with the formulations set forth in Tables 1 and 2 below. Thepolypropylene random copolymer used in the compositions was Pro-faxSA849 polypropylene random copolymer from LyondellBasell Polymers, whichhad an initial Melt Flow Rate of approximately 12 g/10 min. The1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol (referred to as“C.A. X” in the tables that follow) was synthesized in the applicant'slaboratory. 2,3-Dihydroxypropyl octadecanoate was obtained from acommercial source. The product contained approximately 86%2,3-dihydroxypropyl octadecanoate, with the balance being related estercompounds.

TABLE 1 General formulation for Samples 1A-2J. Component AmountPolypropylene random copolymer flake 1,000 g  Acid Scavenger (CalciumStearate) 0.40 g Primary Antioxidant (Irganox ® 1010) 0.50 g SecondaryAntioxidant (Irgafos ® 168) 1.00 g C.A. X As noted in Table 2 below2,3-Dihydroxypropyl octadecanoate As noted in Table 2 below

TABLE 2 Amounts of Compound X and Compound Y used in Samples 1A-2J.Amount of 2,3-Dihydroxypropyl Sample Amount of C.A. X (g) octadecanoate(g) 1A 0 0 1B 0 0.50 1C 0 1.00 2A 1.00 0.0 2B 1.25 0 2C 1.00 0.05 2D1.00 0.1 2E 1.00 0.5 2F 1.00 0.75 2G 1.00 1.0 2H 1.00 1.25 2I 1.00 1.52J 1.00 2.0

Each of the polypropylene random copolymer compositions was compoundedby blending the components in a Henschel high intensity mixer forapproximately 1 minute at a blade speed of approximately 2,100 rpm. Thesamples were then melt compounded on a Deltaplast single screwcompounding extruder with a 25 mm screw diameter and length/diameterratio of 30:1. The barrel temperature was ramped from about 200° C. toabout 230° C. using six heating zones. The extrudate (in the form astrand) for each sample was cooled in a water bath and subsequentlypelletized.

Pellets of each of the resulting polyolefin compositions were moldedinto plaques with dimensions of approximately 51 mm×76 mm with athickness of 1.27 mm using an Arburg 25 ton injection molder. All molderbarrel zones were set to 230° C., and the mold was cooled to 21° C.Plaque dimensions were verified with a micrometer after aging for 24hours. The haze of the plaques was measured in accordance with ASTMStandard D1103-92 using a BYK-Gardner Haze-Guard Plus. The measuredpercent haze for the plaques is reported in Table 3 below.

TABLE 3 Haze values of plaques made from Samples 1A-2J. Sample Haze (%)1A 45 1B 46 1C 46 2A 31 2B 23 2C 28 2D 27 2E 24 2F 22 2G 21 2H 20 2I 192J 17

As can be seen from the data shown in Table 3, polypropylene randomcopolymer compositions containing only 2,3-Dihydroxypropyl octadecanoate(samples 1B and 1C) do not have a lower haze than a comparable sample(1A) that contains no 2,3-Dihydroxypropyl octadecanoate. However, when1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol (“C.A. X”) wasadded to the same resin (samples 2A, 2B, and 2C), the haze wassignificantly lower than sample 1A. So, C.A. X clarifies polypropyleneand 2,3-Dihydroxypropyl octadecanoate does not clarify polypropylene.Surprisingly, when both 2,3-Dihydroxypropyl octadecanoate and C.A. X areadded to polypropylene, the haze is noticeably lower. Comparing the Hazeof Sample 2A to Samples 2D-2J, it can be seen that the addition of2,3-Dihydroxypropyl octadecanoate can lower the haze of polypropylene byas much as 45%.

Example 2

This example demonstrates the production of a polyolefin composition asdescribed above and the properties of the resulting polyolefincomposition.

Ten one-kilogram batches of a polypropylene random copolymer composition(Samples 3A-3J) were compounded in accordance with the formulations setforth in Tables 4 and 5 below. The polypropylene random copolymer andtesting conditions were the same as those used in Example 1. An“Enhancing Additive” (E.A.) was added to each of the compositions. E.A.1 was the same 2,3-dihydroxypropyl octadecanoate used in Example 1. E.A.2 was an amide compound conforming to the structure of Formula (X)wherein each R₁₁ was heptadecan-1-yl and R₁₅ was ethane-1,2,-diyl. E.A.3 was an amide compound conforming to the structure of Formula (I)wherein R₁ was (Z)-8-heptadecen-1-yl. E.A. 4 was an amide compoundconforming to the structure of Formula (I) wherein R₁ was(Z)-12-heneicosen-1-yl.

TABLE 4 General formulation for Samples 3A-3J. Component AmountPolypropylene random copolymer flake 1,000 g  Acid Scavenger (CalciumStearate) 0.40 g Primary Antioxidant (Irganox ® 1010) 0.50 g SecondaryAntioxidant (Irgafos ® 168) 1.00 g C.A. X As noted in Table 5 belowEnhancing Additive As noted in Table 5 below

TABLE 5 Amounts of C.A. X and Enhancing Additive used in Samples 3A-3J.Amount of Amount of Amount of Amount of Amount of Sample C.A. X (g) E.A.1 (g) E.A. 2 (g) E.A. 3 (g) E.A. 4 (g) 3A 1.00 0 1.0 0 0 3B 1.00 0 0 1.00 3C 1.00 0 0 0 1.0 3D 1.25 1.25 0 0 0 3E 1.25 0 1.25 0 0 3F 1.25 0 01.25 0 3G 1.50 1.5 0 0 0 3H 1.50 0 1.5 0 0 3I 1.50 0 0 1.5 0 3J 1.50 0 00 1.0

The measured percent haze for the plaques are reported in Table 6 below.

TABLE 6 Haze values of plaques made from Samples 3A-3J. Sample Haze (%)3A 21 3B 22 3C 20 3D 17 3E 17 3F 17 3G 14 3H 14 3I 14 3J 13

As can be seen from the data shown in Tables 2 and 6, the amide-basedenhancing additives improve the performance of C.A. X. When either theamide-based or the ester-based enhancing additives are added to C.A. X,the haze is significantly lower than the haze of an identical level ofneat C.A. X without the enhancing additive. For example, the haze ofSample 3C is 35% lower than the haze of Sample 2A.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the subject matter of this application (especiallyin the context of the following claims) are to be construed to coverboth the singular and the plural, unless otherwise indicated herein orclearly contradicted by context. The terms “comprising,” “having,”“including,” and “containing” are to be construed as open-ended terms(i.e., meaning “including, but not limited to,”) unless otherwise noted.Recitation of ranges of values herein are merely intended to serve as ashorthand method of referring individually to each separate valuefalling within the range, unless otherwise indicated herein, and eachseparate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the subject matter of theapplication and does not pose a limitation on the scope of the subjectmatter unless otherwise claimed. No language in the specification shouldbe construed as indicating any non-claimed element as essential to thepractice of the subject matter described herein.

Preferred embodiments of the subject matter of this application aredescribed herein, including the best mode known to the inventors forcarrying out the claimed subject matter. Variations of those preferredembodiments may become apparent to those of ordinary skill in the artupon reading the foregoing description. The inventors expect skilledartisans to employ such variations as appropriate, and the inventorsintend for the subject matter described herein to be practiced otherwisethan as specifically described herein. Accordingly, this disclosureincludes all modifications and equivalents of the subject matter recitedin the claims appended hereto as permitted by applicable law. Moreover,any combination of the above-described elements in all possiblevariations thereof is encompassed by the present disclosure unlessotherwise indicated herein or otherwise clearly contradicted by context.

What is claimed is:
 1. A polyolefin composition comprising: (a) apolyolefin polymer; (b)1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol, wherein the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol is a powdercomprising a plurality of particles, and the plurality of particles havea D[4,3] of about 40 μm or less and a D₉₀ of about 80 μm or less; and(c) an ester composition comprising ester compounds, wherein at least aportion of the ester compounds are an ester of 1,2,3-propanetriol and atleast one fatty acid selected from the group consisting of C₁₄-C₂₂ fattyacids, wherein the ester composition comprises about 80% or moremonoester compounds, and wherein the polyolefin composition has a meltflow rate of 4 to about 50 g/10 min as determined using Procedure B ofASTM Standard D1238-10.
 2. The polyolefin composition of claim 1,wherein the 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol ispresent in the polyolefin composition in an amount of about 250 ppm toabout 3,000 ppm.
 3. The polyolefin composition of claim 2, wherein the1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol is present inthe polyolefin composition in an amount of about 500 ppm to about 2,000ppm.
 4. The polyolefin composition of claim 1, wherein the estercomposition is present in the polyolefin composition in an amount ofabout 50 ppm to about 5,000 ppm.
 5. The polyolefin composition of claim4, wherein the ester composition is present in the polyolefincomposition in an amount of about 100 ppm to about 3,000 ppm.
 6. Thepolyolefin composition of claim 1, wherein the fatty acid is a saturatedfatty acid.
 7. The polyolefin composition of claim 1, wherein the fattyacid is selected from the group consisting of C₁₆-C₁₈ fatty acids. 8.The polyolefin composition of claim 1, wherein the ester compositioncomprises 2,3-dihydroxypropyl octadecanoate.
 9. The polyolefincomposition of claim 8, wherein the ester composition comprises about50% or more of 2,3-dihydroxypropyl octadecanoate.
 10. The polyolefincomposition of claim 1, wherein the only clarifying agent present in thecomposition is 1,3:2,4-bis-O-[(3,4-dichlorophenyl)methylene]-D-glucitol.